A solid state and theoretical study of the solvent effects controlling the mono- and di-lithiation of aromatic primary amines

D R Armstrong, S C Ball, D Barr, W Clegg, D J Linton, L C Kerr, D Moncrieff, P R Raithby, R J Singer, R Snaith, D Stalke, A E H Wheatley, D S Wright

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11 Citations (Scopus)

Abstract

Reaction of 1-naphthylamine, 4-tritylaniline or 4-methylaniline with two equivalents of (BuLi)-Li-n in Et2O or thf affords rare geminal N,N-dilithiates of general formula (L)(n).((LiNAr)-N-2)(10) (L = Et2O, n = 6, Ar = 1-C10H7 1, C6H4-4-CPh3 2; L = thf, n = 10, Ar = C6H4-4-Me 3). X-Ray crystal structure analyses reveal that the core (Li14N10)(6-) frameworks consist of two fused rhombic dodecahedra. Ab initio M. O. calculations on the mono- and di-lithiation of 1-naphthylamine and 4-methylaniline suggest that the selectivity with which polymetallation occurs is solvent dependent and so help to rationalise the experimentally observed structures.
Original languageEnglish
Pages (from-to)2505-2511
Number of pages7
JournalJournal of the Chemical Society: Dalton Transactions
Issue number12
DOIs
Publication statusPublished - 2002

Keywords

  • reactivity
  • amide ladder structures
  • tetrahydrofuran
  • chemistry
  • ray crystal-structure
  • basis sets
  • cage molecule
  • ring-stacking
  • lithium anilide
  • tmeda = me2nch2ch2nme2

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    Armstrong, D. R., Ball, S. C., Barr, D., Clegg, W., Linton, D. J., Kerr, L. C., Moncrieff, D., Raithby, P. R., Singer, R. J., Snaith, R., Stalke, D., Wheatley, A. E. H., & Wright, D. S. (2002). A solid state and theoretical study of the solvent effects controlling the mono- and di-lithiation of aromatic primary amines. Journal of the Chemical Society: Dalton Transactions, (12), 2505-2511. https://doi.org/10.1039/b107970k